JPH11171925A - Propylene polymer - Google Patents

Abstract

(A) (A) Isopropylene triad fraction of 98% or more as measured by ¹³ C-NMR of a propylene unit chain portion comprising a head-tail bond, (B) ¹³ C-NMR 2,1 of propylene monomer in total propylene insertion
The proportion of the positionally irregular units based on the insertion is 0.03% or less, the proportion of the positionally irregular units based on the 1,3-insertion of the propylene monomer is 0.06% or more, and (C) the weight average molecular weight is 10,000 to 1,000,000, (D) melting point is 1
A propylene polymer having a temperature of 60 ° C. or higher. [Effect] A propylene-based polymer having high transparency and high impact strength is provided despite excellent rigidity, heat resistance, moldability, and gloss.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has an extremely high isotactic triad fraction and has a specific amount of regio-irregular units based on 2,1-insertions and regio-irregular units based on 1,3-insertions. And a novel propylene-based polymer having a specific weight average molecular weight.

[0002]

2. Description of the Related Art Propylene polymers are rigid, heat-resistant,
It is noted for its excellent moldability, transparency and chemical resistance, and is widely used for various applications such as various industrial parts materials, containers, films and fibers.

[0003]

However, the conventional propylene-based polymer is not always sufficient in transparency, impact resistance and the like depending on the use. For this reason, the appearance of a propylene-based polymer which is not only excellent in rigidity, heat resistance, moldability and chemical resistance, but also excellent in transparency and impact strength is desired.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made to increase the isotactic triad fraction in a propylene-based polymer and to increase the specific amount of 2,1-insertion. Position irregular units based on
Novel propylene-based polymer with a specific weight-average molecular weight having positionally irregular units based on insertion has high transparency and impact resistance despite excellent rigidity, heat resistance, moldability and gloss. It was found that it was completed.

[0005] The propylene-based polymer of the present invention comprises (A) a ¹³ C-NM of a propylene unit chain comprising a head-to-tail bond.
Isotactic triad fraction measured by R is 98%
As described above, (B) the proportion of the position irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion was 0.03% or less and the 1,3-insertion of the propylene monomer was measured by ¹³ C-NMR. Is 0.06% or more, and (C) the weight average molecular weight Mw is 1000
0 to 1,000,000, and (D) a propylene-based polymer having a melting point of 160 ° C. or higher. This will be described in detail below.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION <Propylene-based polymer> The propylene-based polymer according to the present invention comprises an isotactic triad fraction ( ^13C -NMR) of a propylene unit chain composed of head-to-tail bonds measured by ¹³ C-NMR. That is, out of three arbitrary propylene monomer units in the polymer chain, the ratio of three propylene units in which each propylene unit is bonded head-to-tail and the direction of methyl branch in the propylene unit is the same is 98%. Or more, preferably 99% or more. The isotactic triad fraction is hereinafter referred to as m
It may be written as m fraction.

The ¹³ C-NMR spectrum can be measured, for example, by the following method. ^{The 13} C-NMR spectrum is 10
100 to 500 in a sample tube for mmΦ NMR measurement
mg sample was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and then measured at 130 ° C. by a complete proton decoupling method. The measurement was performed at a flip angle of 60 ° and repeated for 5 seconds.

The chemical shift is defined as 21.8 ppm of the methyl group in the third unit of five propylene units in which head-to-tail bonds are formed and the branch directions of the methyl groups are the same, and the chemical shift of other carbon peaks is set. Is based on this. According to this standard, the peak based on the methyl group of the second unit in three chains of propylene units represented by PPP [mm] is 2
In the range of 1.3 to 22.2 ppm, the peak based on the methyl group of the second unit in the 3 chains of propylene units represented by PPP [mr] is in the range of 20.5 to 21.3 ppm.
The peak based on the methyl group of the second unit in the three chains of propylene units represented by PPP [rr] is 19.7 to 20.
Appears in the range of 5 ppm. Here, PPP [mm], P
PP [mr] and PPP [rr] are respectively shown as follows.

[0009]

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Furthermore, the propylene polymer of the present invention contains a specific amount of the following structures (I) and (II) containing regiorandom units based on 2,1-insertion and 1,3-insertion of propylene. .

[0011]

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It is generally considered that such a partial structure is caused by positional irregularities generated during the polymerization of a propylene-based polymer. Most of the propylene monomers in this polymer are 1,2-insertions in which the methylene side is bonded to the metal center of the catalyst, but there are also 2,1- or 1,3-insertions depending on the case. 2,1-
The monomers polymerized by insertion form regiorandom units represented by structure (I) in the polymer chain. Also,
The monomer polymerized by the 1,3-insertion forms a position irregular unit represented by the structure (II) in the polymer chain.
Mm in the entire polymer chain of the propylene-based polymer of the present invention.
The fraction is represented by the following equation. By the way, structure (II)
In Example 1, as a result of 1,3-insertion, one methyl group has been lost by an amount corresponding to one.

[0013]

(Equation 1)

In [Equation 1], ΔICH ₃ indicates the area of all methyl groups (19 to 22 ppm). A, A
, A, A, A, A, A, A and A
Are 42.3 ppm, 35.9 ppm and 38.
6 ppm, 30.6 ppm, 36.0 ppm, 31.5
ppm, 31.0 ppm, 37.2 ppm, 27.4 p
pm, and indicates the abundance ratio of carbon shown in the partial structures (I) and (II). The ratio of 2,1-inserted propylene and the ratio of 1,3-inserted propylene with respect to the total propylene insertion can be calculated by the following formula.

[0015]

(Equation 2)

The propylene-based polymer of the present invention, ¹³ C-N
The proportion of regio-irregular units based on 2,1-insertion in the total propylene insertion measured by MR is 0.03% or less.
In the propylene-based polymer of the present invention, the proportion of the position irregular units based on the 1,3-insertion of the propylene monomer is 0.06% or more. However, in consideration of the heat resistance of the propylene-based polymer, it is usually 0.06 to 1.00%, preferably 0.06 to 0.5%, more preferably 0.06 to 0.5%.
The range is 0.2%.

The weight average molecular weight of the propylene polymer of the present invention is from 10,000 to 1,000,000, preferably from 50,000 to 800,000, particularly from 100,000 to 800,000.
000. The weight average molecular weight can be measured by, for example, gel permeation chromatography. or,
The propylene-based polymer of the present invention has a melting point of 160 ° C. or higher, and for this measurement, for example, DSC or the like is used.

The propylene-based polymer of the present invention may be a homopolymer of propylene, or satisfy the conditions (A) and (B) relating to the propylene insertion form, and a small amount of an α-olefin other than propylene (including ethylene). May be an α-olefin copolymer in which propylene is copolymerized in an amount of up to 6.0% with respect to propylene, for example.

<Production of Propylene Polymer> The method for producing a propylene polymer according to the present invention is not particularly limited as long as it provides a propylene homopolymer or copolymer satisfying the above-mentioned physical properties. Among them, a catalyst system suitable for producing the polymer of the present invention is a metallocene-based catalyst. As a catalyst system to be used, for example, an essential component: at least one metallocene compound, an essential component: [-1] aluminum oxy compound , An ionic compound or Lewis acid capable of cation conversion of a component by reacting with the component [-2], and an optional component: a catalyst system comprising a fine particle carrier (1)
Or at least one metallocene compound, an essential component:
A catalyst system (2) containing an ion-exchange layered compound or inorganic silicate other than silicate, and an optional component: an organoaluminum compound may be mentioned.

Component A component that forms a preferred olefin polymerization catalyst for producing a propylene polymer according to the present invention: One example of a transition metal compound which is a metallocene compound is a transition metal compound represented by the following general formula (I). However, the present invention is not limited to these.

[0021]

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M is a metal selected from titanium, zirconium and hafnium, but is preferably zirconium or hafnium. R independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms including silicon. Indicate (but
When more than one R is present on the same indenyl group, they may be joined together at their ω-end to form a ring with a portion of the indenyl group). Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, and pentyl. Groups, hexyl group, octyl group, benzyl group, phenyl group, tolyl group, xyl group, naphthyl group, butenyl group, trimethylsilyl group, triphenylsilyl group, trifluoromethyl group, pentafluorophenyl group and the like. Among these, a methyl group, an ethyl group, a benzyl group, a phenyl group, a tolyl group, a xyl group, a naphthyl group and the like are preferable.

When a plurality of Rs are present, two (or an integer multiple thereof) may be bonded to each other at each ω-terminal. Specific examples of such a divalent group consisting of two Rs bonded at the ω-terminal include, for example, ethylene, trimethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,2-dimethyltetramethylene, -Trimethylsilyltetramethylene, 2
-Trimethylsilyltetramethylene, 1,3-butadiene-1,4-diyl, 1,3-pentadiene-1,5-
Diyl, 2-methyl-1,3-butadiene-1,4-diyl, 1-phenyl-1,3-butadiene-1,4-diyl, 2-phenyl-1,3-butadiene-1,4-diyl and the like Is mentioned.

A each independently represents an integer of 0 or more and 3 or less. It is preferably an integer of 0 or more and 2 or less.
The substitution position is optional, but may be the 1-position, 1'-position, 2
It is preferred that the position is 2 ', 3', 3 ', or any combination thereof. Q represents a divalent hydrocarbon residue having 1 to 30 carbon atoms or a hydrocarbon residue containing silicon or germanium. Specific examples include methylene, dimethylmethylene, ethylene, tetramethylethylene, trimethylene, tetramethylene, pentamethylene,
Dimethylsilylene, (methyl) (phenyl) silylene,
Examples include diphenylsilylene, tetramethyldisilylene, hexamethyltrisilylene, dimethylgermylene and the like. Of these, dimethylsilylene, (methyl) (phenyl) silylene, diphenylsilylene, dimethylgermylene and the like are preferable.

X and Y each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon residue having 1 to 20 carbon atoms, or a hydrocarbon residue containing nitrogen, oxygen, silicon or phosphorus. Examples of the halogen atom include chlorine, bromine and iodine. Specific examples of the monovalent hydrocarbon residue having 1 to 20 carbon atoms include a methyl group, an ethyl group, and n-
Propyl group, i-propyl group, cyclopropyl group, n-
Butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, benzyl group, phenyl group, tolyl group, xyl group, naphthyl group,
Butenyl group and the like. The oxygen atom of the oxygen-containing hydrocarbon group may be any of an alkoxy bond, an ether bond, a ketone bond and an ester bond, and the number thereof may be one or more, but a preferable one has one oxygen atom. Especially an alkoxy group of an alkoxy bond. The nitrogen atom of the nitrogen-containing hydrocarbon group may be any of an amino bond, a nitrile bond and the like, and the number of nitrogen atoms may be one or more. Preferred are those having one nitrogen atom, particularly those having an amino bond. , An alkylamino group. The silicon-containing hydrocarbon group may have one or more silicon atoms, but is preferably one having one silicon atom, particularly an alkylsilyl group. The silicon-containing oxygen-containing hydrocarbon group may have one or more silicon and oxygen atoms, but is preferably one having one silicon atom and one oxygen atom, particularly an alkylsiloxy group. The phosphorus-containing hydrocarbon group may have one or more phosphorus atoms, but is preferably one having one phosphorus atom, particularly an alkyl phosphide group. Examples of the transition metal compound which is a metallocene compound used for producing the propylene-based polymer of the present invention include the following in the general formula [I].

NO. Q Me XYR 1 Me2Si Zr Cl Cl 1,1′-diphenyl-3,3′-dimethyl 2 Me2Si Zr Cl Cl 1,1′-diphenyl-3,3′-diethyl 3 Me2Si Zr Cl Cl 1 , 1'-Di (3-methylphenyl) -3,3'-dimethyl 4 Me2Si Zr Cl Cl 1,1'-Di (3-methylphenyl) -3,3'-diethyl 5 Me2Si Zr Cl Cl 1,1 '-Di (3-chlorophenyl) -3,3'-dimethyl 6 Me2Si Zr Cl Cl 1,1'-Di (4-methylphenyl) -3,3'-dimethyl 7 Me2Si Zr Cl Cl 1,1'- Di (4-trifluoromethylphenyl) -3,3'-dimethyl 8 Me2Si Zr Cl Cl 1,1'-Di (3,5-dimethylphenyl) -3,3'-dimethyl 9 Me2Si Zr Cl Cl 1,1 '-Di [2- (4-methylnaphthyl)]-3,3'-dimethyl 10 Me2Si Zr Cl Cl 1,1'-diphenyl-3,3', 7,7'-tetramethyl 11 MePhSi Zr Cl Cl 1 , 1'-diphenyl-3,3'-dimethyl 12 MePhSi Zr Cl Cl 1,1'-diphenyl-3,3'-diethyl 13 MePhSi Zr Cl Cl 1,1'-di (3-methylphenyl) -3, 3'-Dimethyl 14 MePhSi Zr Cl Cl 1,1'-Di (3-methylphenyl) -3,3'-diethyl 1 5 MePhSi Zr Cl Cl 1,1'-di (3-chlorophenyl) -3,3'-dimethyl 16 MePhSi Zr Cl Cl 1,1'-di (4-methylphenyl) -3,3'-dimethyl 17 MePhSi Zr Cl Cl 1,1'-di (4-trifluoromethylphenyl) -3,3'-dimethyl 18 MePhSi Zr Cl Cl 1,1'-di (3,5-dimethylphenyl) -3,3'-dimethyl 19 MePhSi Zr Cl Cl 1,1'-di [2- (4-methylnaphthyl)]-3,3'-dimethyl 20 MePhSi Zr Cl Cl 1,1'-diphenyl-3,3 ', 7,7'- Tetramethyl 21 Ph2Si Zr Cl Cl 1,1'-diphenyl-3,3'-dimethyl 22 Ph2Si Zr Cl Cl 1,1'-diphenyl-3,3'-diethyl 23 Ph2Si Zr Cl Cl 1,1'-di ( 3-methylphenyl) -3,3'-dimethyl 24 Ph2Si Zr Cl Cl 1,1'-di (3-methylphenyl) -3,3'-diethyl 25 Ph2Si Zr Cl Cl 1,1'-di (3- Chlorphenyl) -3,3'-dimethyl 26 Ph2Si Zr Cl Cl 1,1'-di (4-methylphenyl) -3,3'-dimethyl 27 Ph2Si Zr Cl Cl 1,1'-di (4-trifluoro Methylphenyl) -3,3'-dimethyl 28 Ph2Si Zr Cl Cl 1,1'-di (3,5-dimethylphenyl Nyl) -3,3'-dimethyl 29 Ph2Si Zr Cl Cl 1,1'-di [2- (4-methylnaphthyl)]-3,3'-dimethyl 30 Ph2Si Zr Cl Cl 1,1'-diphenyl-3 , 3 ', 7,7'-Tetramethyl 31 Me2Si Zr NMe2 NMe2 1,1'-Diphenyl-3,3'-dimethyl 32 Me2Si Zr NMe2 NMe2 1,1'-Diphenyl-3,3'-diethyl 33 Me2Si Zr NMe2 NMe2 1,1'-di (3-methylphenyl) -3,3'-dimethyl 34 Me2Si Zr NMe2 NMe2 1,1'-di (3-methylphenyl) -3,3'-diethyl 35 Me2Si Zr NMe2 NMe2 1,1'-Di (3-chlorophenyl) -3,3'-dimethyl 36 Me2Si Zr NMe2 NMe2 1,1'-Di (4-methylphenyl) -3,3'-dimethyl 37 Me2Si Zr NMe2 NMe2 1, 1'-Di (4-trifluoromethylphenyl) -3,3'-dimethyl 38 Me2Si Zr NMe2 NMe2 1,1'-Di (3,5-dimethylphenyl) -3,3'-dimethyl 39 Me2Si Zr NMe2 NMe2 1,1'-di [2- (4-methylnaphthyl)]-3,3'-dimethyl 40 Me2Si Zr NMe2 NMe2 1,1'-diphenyl-3,3 ', 7,7'-tetramethyl 41 Me2Si Zr NEt2 NEt2 1,1'-diphenyl-3,3'-dimethyl 42 Me2Si Zr NEt2 NEt2 1,1'-diphenyl-3,3'-diethyl 43 Me2Si Zr NEt2 NEt2 1,1'-di (3-methylphenyl) -3,3'-dimethyl 44 Me2Si Zr NEt2 NEt2 1,1'-di ( 3-Methylphenyl) -3,3'-diethyl 45 Me2Si Zr NEt2 NEt2 1,1'-di (3-chlorophenyl) -3,3'-dimethyl 46 Me2Si Zr NEt2 NEt2 1,1'-di (4- Methylphenyl) -3,3'-dimethyl 47 Me2Si Zr NEt2 NEt2 1,1'-di (4-trifluoromethylphenyl) -3,3'-dimethyl 48 Me2Si Zr NEt2 NEt2 1,1'-di (3,3 5-Dimethylphenyl) -3,3'-dimethyl 49 Me2Si Zr NEt2 NEt2 1,1'-di [2- (4-methylnaphthyl)]-3,3'-dimethyl 50 Me2Si Zr NEt2 NEt2 1,1'- Diphenyl-3,3 ', 7,7'-tetramethyl 51 Me2Si Hf Cl Cl 1,1'-diphenyl-3,3'-dimethyl 52 Me2Si Hf Cl Cl 1,1'-diphenyl-3,3'-diethyl 53 Me2Si Hf Cl Cl 1,1'-di (3-methylphenyl) -3,3'-dimethyl 54 Me2Si Hf Cl Cl 1,1'-di (3-methylphenyl) -3,3'-diethyl 55 Me2Si Hf Cl Cl 1,1'-di (3-chlorophenyl) -3,3'-dim Le 56 Me2Si Hf Cl Cl 1,1'-di (4-methylphenyl) -3,3'-dimethyl 57 Me2Si Hf Cl Cl 1,1'-di (4-trifluoromethylphenyl) -3,3'- Dimethyl 58 Me2Si Hf Cl Cl 1,1'-di (3,5-dimethylphenyl) -3,3'-dimethyl 59 Me2Si Hf Cl Cl 1,1'-di [2- (4-methylnaphthyl)]-3 , 3'-dimethyl 60 Me2Si Hf Cl Cl 1,1'-diphenyl-3,3 ', 7,7'-tetramethyl 61 Me2Ge Zr Cl Cl 1,1'-diphenyl-3,3'-dimethyl 62 Me2Ge Zr Cl Cl 1,1'-diphenyl-3,3'-diethyl 63 Me2Ge Zr Cl Cl 1,1'-di (3-methylphenyl) -3,3'-dimethyl 64 Me2Ge Zr Cl Cl 1,1'-di (3-methylphenyl) -3,3'-diethyl 65 Me2Ge Zr Cl Cl 1,1'-di (3-chlorophenyl) -3,3'-dimethyl 66 Me2Ge Zr Cl Cl 1,1'-di (4 -Methylphenyl) -3,3'-dimethyl 67 Me2Ge Zr Cl Cl 1,1'-di (4-trifluoromethylphenyl) -3,3'-dimethyl 68 Me2Ge Zr Cl Cl 1,1'-di (3 , 5-Dimethylphenyl) -3,3'-dimethyl 69 Me2Ge Zr Cl Cl 1,1'-di [2- (4-methylna Fthyl)]-3,3'-dimethyl 70 Me2Ge Zr Cl Cl 1,1'-diphenyl-3,3 ', 7,7'-tetramethyl

Although these transition metal compounds may have optical isomers, it is preferable to use a racemic type when producing the propylene polymer of the present invention.

The component ingredients, [- 1] or aluminum oxy compound as a, [- 2], and the component is cationic convertible ionic compound or Lewis acid reacts with the component as a. Here, some Lewis acids can be regarded as “ionic compounds that can react with components and convert components into cations”.
And "ionic compounds capable of reacting with the components to convert the components into cations". Specific examples of the aluminum oxy compound include compounds represented by the following general formulas [II], [III] or [IV].

[0029]

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In each of the above formulas, R ¹ represents a hydrogen atom or a hydrocarbon residue, preferably a C 1-10, particularly preferably a C 1-6 hydrocarbon residue. The plurality of R ¹ may be the same or different. p is 0
40, preferably an integer of 2 to 30. General formula (II)
And [III] are compounds also called alumoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum and water And methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane. Of these, methylalumoxane and methylisobutylalumoxane are preferred.

A plurality of these alumoxanes may be used in each group or in each group. The alumoxane may be prepared by a known method, and examples of the method include the following methods. (A) A method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene, or ether. (B) A method of reacting with a salt hydrate having trialkylaluminum and water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like. (D) A method in which trimethylaluminum and triisobutylaluminum are mixed and directly reacted with water using an appropriate organic solvent such as toluene, benzene or ether. (E) A method in which trimethylaluminum and triisobutylaluminum are mixed and heated and reacted with a salt hydrate having water of crystallization, for example, copper sulfate, aluminum sulfate and a hydrate. (F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum. (G) A method of synthesizing methylalumoxane and isobutylalumoxane by a known method, mixing predetermined amounts of these two components, and causing a heat reaction. (H) A salt having crystallization water, such as copper sulfate pentahydrate, is added to an aromatic hydrocarbon solvent such as benzene or toluene.
A method of reacting with trimethylaluminum under a temperature of about 40 ° C.

The amount of water used in the reaction is usually 0.5 to 1.5 in molar ratio to trimethylaluminum.
The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer. General formula (I
The compound represented by the formula V] is a 10: 1 to 1: 1 (molar ratio) of one kind of trialkylaluminum or two or more kinds of trialkylaluminums and an alkylboronic acid represented by the following general formula (V). Obtained by the reaction of In the general formula (V), R ² represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group.

[0033]

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Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 Reactant Examples of the ionic compound capable of reacting with a component to convert the component into a cation include a compound represented by the general formula [VI].

[0035]

[K] ^{e +} [Z] ^e- [VI]

In the general formula [VI], K is an ionic cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, cations of metals which are easily reduced by themselves, cations of organic metals, and the like can also be mentioned. Specific examples of the above cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N
-Dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium and silver Ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion and the like.

Z in the above general formula [VI] is an ionic anion component, which is a component (generally a non-coordinating component) that becomes a counter anion to the converted cation species. Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, an organic antimony compound anion, and the like, and specific examples include the following compounds. .

(A) Tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5-di (t- Butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3
4,5-trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc. (C) tetraphenylgallium, tetrakis (3,4,
5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl)
Gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorous, etc. (e) tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetraphenyl antimony, tetrakis (penta) (G) decaborate, undecaborate, carbado decaborate, decachloro decaborate, etc.

Examples of Lewis acids, particularly Lewis acids whose components can be converted into cations, include various organic boron compounds,
Examples thereof include metal halide compounds, solid acids, and ion-exchanged layered silicates. Specific examples thereof include the following compounds. (A) Organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide Metal halide compounds such as, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium hydride, magnesium hydride, magnesium hydride, magnesium alkoxide, magnesium alkoxide, etc. c) Solid acids such as silica-alumina and alumina

[0040]component The fine particle carrier as an optional component
5μ to 5mm, preferably 10μ
Granular or particulate carrier having a particle size of ~ 2 mm
It is. Examples of the inorganic carrier include, for example, SiO 2_Two,
Al_TwoO_Three, MgO, ZrO, TiO_Two, B_TwoO_Three, Z
oxides such as nO, SiO_Two-MgO, SiO_Two-Al
_TwoO_Three, SiO_Two-TiO_Two, SiO_Two−Cr_TwoO_Three,
SiO_Two-Al_TwoO_Three-Composite oxides such as MgO;
Can be

As the above organic carrier, for example, ethyl
Propylene, 1-butene, 4-methyl-1-pentene
(Co) polymers of α-olefins having 2 to 14 carbon atoms, such as
Aromatic unsaturated hydrocarbons such as styrene and divinylbenzene
Fine particle carrier of porous polymer composed of (co) polymer etc.
Is mentioned. Their specific surface area is 20-1000m ^Two
/ G, preferably 50-700 m^Two/ G, pore volume
The product is 0.1cm^Two/ G or more, preferably 0.3 cm^Two/
g, more preferably 0.8 cm^Two/ G or more.

The catalyst system (1) includes, as optional components other than the fine particle carrier, for example, active hydrogen-containing compounds such as water, methanol, ethanol, and butanol, ethers, esters, and the like.
Electron donating compounds such as amines, phenyl borate, dimethylmethoxyaluminum, phenylphosphite, tetraethoxysilane, alkoxysilane compounds such as diphenyldimethoxysilane, trimethylaluminum, triethylaluminum, tri-lower alkylaluminum such as triisobutylaluminum, Dimethylaluminum chloride, diethylaluminum chloride, halogen-containing alkylaluminums such as diisobutylaluminum chloride, alkylaluminum hydrides such as diethylaluminum hydride, diethylaluminum ethoxide,
Alkoxy-containing alkylaluminums such as dimethylaluminum butoxide, and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide may be used.

In the catalyst system (1), an aluminum oxy compound, an ionic compound capable of reacting with a component to convert the component into a cation, or a Lewis acid is used alone as a component, and these three components are appropriately combined. May be used. One or more of the above-mentioned lower alkylaluminum, halogen-containing alkylaluminum, alkylaluminum hydride, alkoxy-containing alkylaluminum, and aryloxy-containing alkylaluminum are optional components. Catalyst system (1) in combination with convertible ionic compound or Lewis acid
It is preferable that

The handling of each component in the catalyst system (1) is as follows.
It can be prepared by bringing the components into contact with each other in the presence or absence of the monomer to be polymerized inside and outside the polymerization tank. That is, the components and the components and the components and the like as necessary may be separately introduced into the polymerization tank, or the components and the components may be brought into contact with each other in advance and then introduced into the polymerization tank. Alternatively, the components and the mixture of the components may be impregnated into the components and then introduced into the polymerization tank.

The contact of each component is performed in an inert gas such as nitrogen.
It may be carried out in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene and the like. The contact temperature is
The reaction is carried out between -20 ° C and the boiling point of the solvent, particularly preferably between 0 ° C and the boiling point of the solvent. The catalyst thus prepared may be used for polymerization of propylene or the like without washing after preparation, or may be used after washing. Further, new components may be used in combination as needed after preparation.

When the components, the components and the components are brought into contact with each other in advance, α
A so-called prepolymerization for polymerizing a part of the olefin may be performed. That is, before polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-
Olefins such as methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, and styrene are preliminarily polymerized, and if necessary, the prepolymerized product washed can be used as a catalyst.

This preliminary polymerization is mild in an inert solvent.
It is preferable to carry out the reaction under the conditions, and the amount of 0.1 g per 1 g of the solid catalyst.
Polymerization of 01 to 1000 g, preferably 0.1 to 100 g
It is desirable to do so that the body produces. Ingredients and
The amounts of the components used are arbitrary. For example, in the case of solvent polymerization,
The amount of the component used is 10 as transition metal atoms.^-7-10^TwoMi
Lmol / l, even 10 ^-Four~ 1 mmol / l
It is preferably within the range of torr. Aluminum oxy compound
The molar ratio of Al / transition metal is usually 10 to 10000
0, preferably 100 to 20,000, more preferably 1
The range is from 00 to 10,000. On the other hand,
When an ionic compound or Lewis acid is used, the transition gold
Their molar ratio to the genus is usually 0.1 to 1000, preferably
Preferably from 0.5 to 100, more preferably from 1 to 50
Range.

Next, the catalyst system (2) will be described. This catalyst system contains at least one metallocene compound selected from the above-mentioned transition metal compounds, an essential component: an ion-exchange layered compound other than silicate or an inorganic silicate, and an optional component: an organoaluminum compound.

Ingredients: As an ion-exchange layered compound or an inorganic silicate ion-exchanged layered compound, hexagonal close-packed type, antimony type, CdCl ₂ type, Cd
Ionic crystalline compounds can be mentioned having a layered crystal structure of type _2, etc. I, specific examples thereof, α-Zr (HAsO
₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr
(KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ ,
α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO
₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti
(HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O
And crystalline acid salts of polyvalent metals.

The above-mentioned ionic exchangeable layered compound may be subjected to a salt treatment and / or an acid treatment, if necessary, and then used for the polymerization of propylene. In the state where neither salt treatment nor acid treatment has been performed, the ion-exchangeable layered compound except silicate is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, The contained ions are exchangeable.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may use synthetic products, or may use naturally occurring minerals. Specific examples of these include allophane group such as allophane, dickite, nacrite, kaolinite, kaolin group such as anoxite, metahalloysite, halloysite group such as halloysite, chrysotile, lizardite, serpentine group such as antigorite, Montmorillonite,
Vermiculite minerals, such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite, illite, sericite,
Examples include mica minerals such as marine green stone, attapulgite, sepiolite, palygorskite, bentonite, kibushi clay, gailome clay, hisingelite, pyrophyllite, and ryokudeite group. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Examples of the inorganic silicate include kaolins such as deckite, nacrite, kaolinite and anoxite, halosites such as metahalosite and halosite, serpentine groups such as chrysotile, risaldite and antigolite, and montmorillonite. , Soconite, Beiderite,
Non-tronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite,
Preferred are mica minerals such as illite, sericite and chlorite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite, and vermiculite such as smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, and vermiculite. Minerals, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite are more preferred. These may be used as they are without performing any special treatment, or may be used after performing a treatment such as ball milling and sieving. Further, they may be used alone or in combination of two or more.

The acid strength of the solid of the ion-exchange layered compound and the inorganic silicate can be changed by salt treatment and / or acid treatment. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

For compounds not subjected to the above pretreatment,
More than 40% of exchangeable metal cations contained in
Salts and / or acids preferably having 60% or more of the following
Prefer ion exchange with more dissociated cations
No. Salts used for the above-mentioned ion exchange are selected from groups 1 to 14
Containing cations of atoms selected from the group consisting of
A cation of a group 1-14 atom,
Selected from the group consisting of halogen atoms, inorganic acids and organic acids
Compound comprising at least one anion
And more preferably a cation of a group 2-14 atom and C
1, Br, I, F, PO_Four, SO_Four, NO_Three, CO_Three,
C_TwoO_Four, ClO _Four, OOCCH_Three, CH_ThreeCOCHC
OCH_Three, OCI_Two, O (NO_Three)_Two, O (ClO_Four)
_Two, O (SO_Four), OH, O_TwoCl_Two, OCI_Three, OO
CH, OOCCH_TwoCH_ThreeFrom the group consisting of
It is a compound consisting of at least one kind of anion. Also,
Two or more of these salts may be used in combination.

The acid used for the above ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.
Two or more kinds may be used in combination. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of performing the salt treatment and the acid treatment simultaneously, and a method of combining these There is. Preferably, after the salt treatment, the salt treatment and the acid treatment are performed simultaneously. The acid treatment has an effect of removing impurities on the surface and eluting a part of cations such as Al, Fe, Mg, and Li having a crystal structure.

The treatment conditions with salts and acids are arbitrary, but usually the salt and acid concentrations are 0.1 to 30% by weight,
The treatment temperature ranges from room temperature to the boiling point of the solvent used, and the treatment time ranges from 5 minutes to 2 minutes.
It is preferably performed for 4 hours under conditions that elute at least a part of the compound to be treated. Further, salts and acids are generally used as an aqueous solution. The above salt treatment and / or
Alternatively, when an acid treatment is performed, shape control may be performed by pulverization, granulation, or the like before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination.
The component thus obtained preferably has a pore volume of not less than 0.1 cc / g, more preferably from 0.3 to 5 cc / g, having a pore volume of a radius of 20 ° or more measured by a mercury intrusion method. Such components typically include adsorbed water and interlayer water. Here, the adsorbed water refers to water adsorbed on the surface of an ion-exchangeable layered compound other than silicate or an inorganic silicate or a crystal fracture surface, and the interlayer water is water existing between crystal layers.

In the present invention, the components are preferably used after removing the adsorbed water and interlayer water as described above. The method of dehydration is optional, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is in a temperature range in which adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable. Heating time is 0.5
The time is at least one hour, preferably at least one hour. At that time, the water content of the component after dehydration and drying may be 3% by weight or less when the water content when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight. preferable. In the present invention, the water content is 3
When a component adjusted to not more than% by weight is used, it is important that the component is treated so as to maintain the same water content even when it comes into contact with an essential component and an optional component described later.

[0058] as component optional components, an example of the organic aluminum compound is represented by the following general formula (VII).

[0059]

Embedded image AlR _a P _3-a (VII)

In the general formula (VII), R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents a hydrogen atom, a halogen atom, or an alkoxy group, and a is 0 <a ≦ 3. Examples of the organoaluminum compound represented by the general formula (VII) include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum, and halogen or alkoxy-containing compounds such as diethylaluminum monochloride and diethylaluminum monomethoxide. Alkyl aluminum is mentioned. Of these, trialkylaluminum is preferred. In the catalyst system (2), an aluminoxane such as methylaluminoxane may be used as a component.

The catalyst system (2) can be prepared in the same manner as in the case of the catalyst system (1). At this time, the method of contacting the essential component and the component with the optional component is optional,
The following method can be exemplified. a) bringing the components into contact with each other; b) Add the components after contacting the components. c) Add the components after contacting the components. d) Add the components after contacting the components. In addition, the three components may be contacted simultaneously.

When the above components are contacted, the catalyst system (1)
May be allowed to coexist, or may be brought into contact with the fine particle carrier after the above components are brought into contact. The amount of each component is usually 0.000 per gram of the component.
1 to 10 mmol, preferably 0.001 to 5 mmol
And the component is 0.01 to 10000 mmol, preferably 0.1 to 100 mmol. The atomic ratio between the transition metal in the component and the aluminum in the component is usually 1: 0.01 to 1,000,000, preferably 1: 0.1.
１００100,000. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. If necessary, a new component may be used, and the amount of the component used in this case is preferably 1: 0 to 10,000 in terms of the atomic ratio of aluminum in the component to transition metal in the component.

In the catalyst system (2), ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl Olefins such as -1-butene, vinylcycloalkane, and styrene may be preliminarily polymerized and, if necessary, washed and used as a catalyst. This preliminary polymerization is preferably carried out under mild conditions in an inert solvent, and 0.01 to 1000 g per 1 g of the solid catalyst,
Preferably, the reaction is carried out so as to produce 0.1 to 100 g of a polymer.

In the method for producing a propylene polymer of the present invention, basically, polymerization or copolymerization may be performed by bringing the above-mentioned catalyst system into contact with an α-olefin. Catalyst system (1)
Or (2) is applied to solvent polymerization using a solvent, and also to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially using no solvent. Further, the polymerization system may be either continuous polymerization or batch polymerization. As a solvent in the solvent polymerization, an inert saturated fatty acid such as hexane, heptane, pentane, cyclohexane, benzene, and toluene or an aromatic hydrocarbon alone or a mixture is used. The polymerization temperature is usually -78 to 250C, preferably -20 to 100C. The polymerization method is optional as long as the propylene-based polymer of the present invention can be obtained.
Polymerizes at the following low temperatures: The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 2000 kgf / cm.
² G, more preferably in the range of normal pressure to 50 kgf / cm ² G. The molecular weight can be adjusted by a known means such as adjustment of temperature and pressure or introduction of hydrogen into the reaction system.

[0065]

The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the present invention. In the examples, the catalyst synthesis step and the polymerization step were all performed in a purified nitrogen atmosphere, and the solvent used was dehydrated by MS-4A and then degassed by bubbling with purified nitrogen. (1) MFR measurement: heat stabilizer (2, 6
6 g of a solution of tert-butylhydroxytoluene (BHT) in acetone (0.6% by weight) were added. Next, after drying the above polymer, the melt indexer (23
(0 ° C.) and left under a load of 2.16 kg for 5 minutes. Thereafter, the extrusion amount of the polymer was measured, and 10
The value was converted to the amount per minute, and the value was used as the MFR value.

(2) Measurement of molecular weight distribution: weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by GPC
It was determined by the ratio (Q value) of (all values in terms of polyethylene). The GPC device is “150CV” manufactured by Waters.
Type "was used. Ortho-dichlorobenzene was used as the solvent, and the measurement temperature was 135 ° C. (3) Measurement of melting point: DSC (TA200 manufactured by DuPont)
0 "), the temperature was raised and lowered once at 10 ° C./minute from 20 to 200 ° C., and the peak was measured at the second temperature rise.

(4) Olsen flexural modulus measurement Specimen width W = 1.50 cm, fulcrum distance S = 3.0 c
m, bending deformation angle Φ = 0.1745, moment M = 6
Under the condition of kg · cm, the indicated value n of a sample having a thickness (d) of about 0.2 cm was measured, the Olsen flexural modulus E was calculated from the following formula, and the average value of the five samples was taken.

[0068]

(Equation 3)

(5) Measurement of Heat Deformation Temperature Measured under conditions of 4.6 kgf / cm ² G and no annealing. Example 1 After replacing the inside of a 1-liter stirred autoclave with nitrogen, 300 ml of hexane was introduced,
After cooling to 0 ° C., 2.04 mmol (converted to Al atom) of methylalumoxane manufactured by Tosoh Akzo was added. Further, 300 ml of propylene was introduced, the internal temperature was 0 ° C., and rac-dimethylsilylenebis [4- {1- (4-methylphenyl) -3-methylindenyl}] zirconium separately introduced into the catalyst feeder. 0.63mg of dichloride
And 1.02 mmol of methylalumoxane (in terms of Al atom) and 10 ml of hexane were pressure-fed into the autoclave with nitrogen to initiate polymerization. Set the temperature in the autoclave to 0
The polymerization was carried out for 2 hours while maintaining the temperature at 0 ° C. After purging propylene, the polymer was transferred to a 2 liter flask under a nitrogen atmosphere, and 600 ml of hexane, 600 ml of methanol,
The mixture was stirred with 50 ml of concentrated hydrochloric acid for 1 hour. After cooling, the content was filtered, and the solid content was washed three times with 400 ml of methanol and once with 400 ml of acetone, and dried under reduced pressure to obtain 14.2 g of a propylene polymer.

The analysis value of this polymer was as follows: the isotactic triad fraction was 99.3%, the proportion of regio-irregular units based on 2,1-insertion was 0.03% or less, and based on 1,3-insertion. The proportion of the positionally irregular units was 0.15%, the melting point by DSC was 164.8 ° C., the weight average molecular weight by GPC was 460000, and the Q value was 2.7.

Example 2 After replacing the inside of a 2-liter stirred autoclave with nitrogen, a toluene diluent of triisobutylaluminum (Tosoh Akzo) 0.3
mmol (in terms of Al atoms) and 2.4 μmmol (in terms of B atoms) of a dilute solution of dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene were introduced. On the other hand, rac-dimethylsilylenebis [4- {1- (4-methylphenyl)-] was added to the catalyst feeder with a rupture disk.
3-methylindenyl}] zirconium dichloride
2 μmmol was introduced diluted with toluene. 1500 ml of propylene was introduced into the autoclave, and the rupture plate was cut at 17 ° C. to initiate polymerization. Polymerization was carried out at a temperature in the range of 11 to 15 ° C. for 3 hours, and 20 ml of ethanol was introduced to terminate the polymerization. After purging propylene, the polymer was transferred to a 2 L flask, 400 ml of hexane and 60 ml of methanol.
The mixture was stirred at 0 ° C. and 10 ml of concentrated hydrochloric acid at 50 ° C. for 3.5 hours. After cooling, the contents were filtered, and the solid content was
After washing three times with 00 ml and once with 500 ml of acetone, drying was performed under reduced pressure to obtain 65 g of a propylene polymer.

The analysis values of this polymer were as follows: the isotactic triad fraction was 98.5%, the proportion of regio-irregular units based on 2,1-insertion was 0.03% or less, and based on 1,3-insertion. The proportion of the positionally irregular units was 0.14%, the melting point by DSC was 162.4 ° C., the weight average molecular weight by GPC was 230,000, the Q value was 1.9, and the MFR was 5.6.

<Example 3> Phosphorus-based antioxidant: Irgafos 168 was added to the propylene polymer obtained in Example 2.
(0.1 part), a phenolic antioxidant: Irganox 1010 (0.1 part) (all manufactured by Ciba Geigy), and calcium stearate (0.05 part) were added.
Knead at 200 ° C for 3 minutes with Labo Plastomill,
Further, pressing was performed at 230 ° C. and 50 kg / cm ² . After the pressed polymer was cut, the Olsen bending elastic modulus was measured to be 12,700 kg / cm ² .

<Example 4> The heat deformation temperature was measured using a polymer kneaded and pressed in the same manner as in Example 3.
19.6 ° C. <Comparative Example 1> As for the polymer analysis value, the isotactic triad fraction was 92.5%, the proportion of the position irregular units based on 2,1-insertion was 0.03% or less, and based on 1,3-insertion. A titanium trichloride-based catalyst having a position irregular unit ratio of 0.03% or less, a melting point of 158.6 ° C. by DSC, a weight average molecular weight by GPC of 340000, a Q value of 5.5, and an MFR of 4.4. The propylene polymer produced in the above was measured for the Olsen flexural modulus in the same manner as in Example 3.
The weight was 100 kg / cm ² . The heat distortion temperature is 10
7.6 ° C.

[0075]

According to the present invention described above, the isotactic triad fraction is high, and the position irregular units based on a specific amount of 2,1-insertion and the position irregular units based on 1,3-insertion A novel propylene polymer having
Propylene polymer having such characteristics is rigid, heat-resistant,
Despite excellent moldability and gloss, it has high transparency and impact strength.

Claims (1)

[Claims] (A) isotactic triad fraction of at least 98% as measured by ¹³ C-NMR of a propylene unit chain portion comprising a head-to-tail bond, and (B) measured by ¹³ C-NMR. 2 of the propylene monomer during the total propylene insertion
The proportion of regio-irregular units based on 1-insertion is 0.03% or less, the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.06% or more, and (C) the weight average molecular weight is 10,000. ~ 1,000,000, (D) melting point is 1
A propylene polymer having a temperature of 60 ° C. or higher.